Manufacture of liquid hydrocarbons



`,\pri121,1942. M, PIER 2,280,258,

' MANUFAGTURE @LIQUID HYDRocARBoNs Filed Mrch 1, 1939 s osugkArok.

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HXDOGEN LINE 'Patented Apr. 2l, 1942 UNITED STATES PATENT' oF'Fics L 'A 2,280,258 A V MANUFACTURE oF LIQUID Hypno- CARBON Heidelberg, Germany, assignor, by

Mathias llier,

mesne asslgnments, to William E. Currie, New

York, N. y.

l Application March 1,1939, Serial No. 259,114

5 Claims.

- The present invention relates to the manuiacture of liquid hydrocarbons. y'

I have found that the pressure hydrogenationl stances, the .conditions of temperature, as for example'from 350 to 510 C., andof pressure, as

for example 20 atmospheres or' more, preferably from 100 to 1000 atmospheres, already known should beusedand as catalysts in particular the oxides, sulphides, halides and phosphates'of the lheavy metals.

The gaseous olefines may, for example, be produced by splitting ,ethane, propane or butane. These gases are available for example in the waste gases of the pressure hydrogenation. Gaseous oleiines obtained by splitting oils may also be used. In order to-avoid undesirable polymerisations, the oleiines are advantageously led directly after their formation to the preheater or to the reaction vessel.

The manner in which the process is carried out will be fully understood from the following description when read with reference ,to the accompanying drawing which is a semi-diagrammatic view insectional elevation of one type of apparatus which is suitable for the purpose.

Referring to the drawing, numeral l designates a line through which middle oil is supplied. This oil is forced by means of pump 2 through a heating coil I. Hydrogen `or a gas rich in free hydrogen is also supplied to heating coil 3 through line'ld. 4The heated mixture of oil, and hydrogen iiows through line 4 into a reaction vessel 5 whichcontains a suitable catalytic material. Products of reaction leave reaction vessel B through line I, pass through a cooler s and then discharge through line Ill into a separator Il wherein gaseous and liquid products may be separated. The liquid products are removed from separator Il through line l2. II'he gaseous products are removed from separator H through line Il and are passed through a scrubber Il wherein the hydrocarbon constituents are separated irom the hydrogen.- The hydrogen leaves the scrubbing means through line I8 and is recycled to heating coil 3. A booster compressor Il is l In Germany March 2, 1938 provided in line I8 to bring the pressure of the recycled hydrogen-containing gases up to the reaction pressure. The hydrocarbon gases which are removed from the gaseous products of reaction in scrubber ll 4and which will consist essentially of propane and butane are drawn through line I5 by means of pump I6 and forced into an olefin` generating means 1. The. olens generated inn generating means l are then passed through line 6 into reaction vessel 5. Additional propane and butane obtained from an extraneous source may be introduced intololeiln generating means I through line I1 by means of pump Ila.

Inthe operation of the process it is preferable to ysupply the olenes to places of the reaction chamber where a considerable splitting has already taken place so that split products reactA with the oleflne's with alkylation and formation of liquid condensation products.` This is the case Y 20 after about the rst quarter and still more after the first third of the reaction zone. The olelines may also be added during or before the preheating, if desired even before the addition of hydrogen. A manner of -Working consists in carrying out the pressure hydrogenation in the presence of small amounts of hydrogen and under suchV a pressure, f. e., of from.20 to 100 atmospheres, thatpractically no consumption' oi hydrogen takesplace; in this case the olefines 0 are preferably added in the presence of hydrogen. 'In some cases it is disadvantageous for the gaseous 'olellnes to contain .dioleflnes It is. however, possible also to use such gases if they are brought into Contact wmf the materia to be hy- 7 drogenated during the main splitting, i. e., after At the places in the reaction vessel where the olenes enter. there may bearranged a layer of r catalysts which promote the alkylation and/or polymerization, as for example phosphoric acids or metal halides. y

The amount of added olene may be varied within wide limits. Generally speaking amounts of from l0 to.200 per cent by weight, with reference to the initial material to be treated, are V used, and in the case of low molecular materials, l as for example benzines, middle 'oils or the like, from about l0 to 50 per cent, and in the case of 55 high molecular weight initial materials, asfor about the rst half of the reaction zone, because example heavy oils, from about 30 to 300 per Example A middle oil obtained by pressure hydrogenation from German crude oils is led'together with hydrogen under a pressure of 200 atmospheres at a temperature'of 410 C. over a mixture consisting of iron sulphide and tungsten sulphide applied to bleaching earth in an amount of 16 per cent. After the first third of the reaction vessel, there is introduced, in an amount of about 30 per cent by weight with reference to the oil, to be treated, a gas containing olefin'es which has been produced under the same pressure by leading a mixture of propane and butane over a dehydrogenating catalyst at 530 C. The temperature in the reaction chamber after the introduction of the olenes is 460 C.

From 100 kilograms of middle oil, 124 kilo- `grams of benzine and middle oil are obtained. The octane number of the benzine is higher than when it prepared in the absence of olenes.

What I claim is:

1. In a. process for the destructive hydrogenation vof hydrocarbon oils which comprises passing a hydrocarbon oil with added hydrogen izing and alkylating catalyst at the point where the said olenes are introduced into the reaction zone.

3. A process as claimed in claim 1, which comprises providing a metal halide as a polymerizing and alkylating catalyst at the 'point where the said olefnes are introduced into the reaction f ione.

4. A? process as claimed in claim l1. which con-l sists in adding said olenes after about one fourth of the length of the reaction zone.

5. A process as claimed in claim 1 in which the gaseous o lens which are added in an amount of at least 10% by weight of the oil being treated are produced by the splitting of hydrocarbons and fed into the hydrogenation step immediately after their production.

. MATHIAS PIER. 

